Modified Ion Exchange Resin and Process for Producing Bisphenols

ABSTRACT

There is provided a modified ion exchange resin catalyst which exhibits higher bisphenols selectivity than the conventional modified ion exchange resins in processes wherein bisphenols are produced by reacting a phenolic compound with ketones, and to provide such a process for producing bisphenols. A modified ion exchange resin is characterized in that at least one compound selected from (A) and (B) shown below is ionically bonded to an acidic functional group of an acidic ion exchange resin: 
 
(A) Compound represented by Formula (1)  
                 
and 
 
(B) Compound represented by Formula (2)

TECHNICAL FIELD

The present invention relates to a modified ion exchange resin catalystand a process for producing bisphenols using the catalyst thereof. Morespecifically, the invention relates to a modified ion exchange resincatalyst which exhibits a high reaction selectivity, and to a processfor producing bisphenols by reacting a phenolic compound with ketones inthe presence of the catalyst.

BACKGROUND ART

Bisphenol A [2,2-bis(4-hydroxyphenyl)propane] is usually produced byreacting phenol with acetone in the presence of a homogeneous acid or asolid acid catalyst. The reaction mixture includes unreacted acetone,unreacted phenol, water thus produced, and other by-products, inaddition to bisphenol A. The main component of the by-products is2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane (hereinafter, referred toas o,p′-BPA), and in addition, it includes trisphenol, a polyphenolcompound, a chroman compound, minute impurities which can causecoloring, and the like.

Examples of a homogeneous acid to be used as a catalyst, includehydrochloric acid, sulfuric acid, and the like. In the case where thehomogeneous acid is used, since it is possible to proceed the reactionwhile precipitating crystals of an adduct of phenol with bisphenol A byreacting them at lower temperatures, bisphenol A can be produced with ahigh conversion of acetone and a high selectivity by decreasing theamount of the by-produced o,p′-BPA as an isomer thereof. However, thecatalyst of the homogeneous acid such as hydrochloric acid requires aprocess for removing the catalyst from a reaction mixture or forneutralizing the catalyst, and thus the operation becomes complicated.Homogeneous dissolution of the acid in the reaction solution furthercauses corrosion of an apparatus or the like. Therefore, expensive andanti-corrosive materials should be used for the reaction apparatus, thusbeing uneconomical.

As a solid acid catalyst, a sulfonic acid-type cation-exchange resin isusually used. The reaction for producing bisphenol A essentiallyproceeds only with an acid catalyst, but if such a solid acid catalystis used, the process in which acetone diffuses from the surface of thecatalyst particles to an active site on the catalyst is involved, andthus gives a lower reaction rate than in the homogeneous system. Thus,there is a general method used for improving the catalytic activity andthe selectivity by allowing a compound containing a mercapto group tocoexist in the reaction system. Specifically, there is a methodcomprising charging a free-type mercapto group-containing compound suchas alkylmercaptan in addition to phenol and acetone which are rawmaterials to a fixed-bed reactor filled with a sulfonic acid-typecation-exchange resin (for example, Patent Document 1: JP-B No.45-10337, Patent Document 2: U.S. Pat. No. 6,414,200), and a methodcomprising covalently bonding a part of sulfonic acid group in asulfonic acid-type cation-exchange resin with a mercaptogroup-containing compound or ionically bonding a part of sulfonic acidgroup in a sulfonic acid-type cation-exchange resin with a mercaptogroup-containing compound (for example, Patent Document 3: JP-B No.46-19953). The method of charging a free-type mercapto group-containingcompound such as alkylmercaptan in addition to phenol and acetone whichare raw materials to a fixed-bed reactor filled with a sulfonicacid-type cation-exchange resin allows specific amount of mercaptogroup-containing compound to be existed in a reaction system at alltimes, and thus gives the advantage of less catalyst degradation.However, there is a concern that the mercapto group-containing compoundmay cause a coloring of bisphenol A, and thus requires a process forremoving and recovering the mercapto group-containing compound.

On the other hand, the method of bonding a part of sulfonic acid groupin a sulfonic acid-type cation-exchange resin with a mercaptogroup-containing compound gives a smaller loss of mercaptogroup-containing compound as compared to the method allowing thefree-type mercapto group-containing compound to be existed in a reactionsystem, and thus is advantageous since there is no need of recoveringthe mercapto group-containing compound. In particular, there isdisclosed in JP-A No. 57-35533 (use of pyridylethanethiol as a mercaptogroup-containing compound, Patent Document 4), JP-A No. 08-187436 (useof N,N,di-substituted mercaptoalkylamine as a mercapto group-containingcompound, Patent Document 5), JP-A No. 08-089819 (use of N,N,N-trimethylmercaptopropyl ammonium as a mercapto group-containing compound, PatentDocument 6), JP-A No. 10-211433 (use of 1,4-dimercaptoalkylpiperidine asa mercapto group-containing compound, Patent Document 7), and U.S Pat.No. 6,414,200 (use of a silicon-containing alkylmercapto compound as amercapto group-containing compound, Patent Document 2), that thereaction rate of acetone is increased by improving the structure of amercapto group-containing compound which to be bonded to a strong-acidion-exchange resin.

Further, there is also a report related to a sulfonic acid-typecation-exchange resin which is an acid catalyst for improving itsactivity which is lower than that of the above-described homogeneousacid. When the particle diameter of used sulfonic acid-typecation-exchange resin is large, the reaction materials do notsufficiently diffuse into the particles, thus a sufficient acetoneconversion cannot be obtained. Accordingly, it is suggested in JP-A No.62-178532 (Patent Document 8) to use a sulfonic acid-typecation-exchange resin in a fine particle or a fine powder having aneffective diameter of 0.3 mm or less. In JP-A No. 6-340563 (PatentDocument 9), the particle diameter of sulfonic acid-type cation-exchangeresin to be used and the distribution degree of the particle diameter islikewise provided, and more preferred range is disclosed. Further, inJP-A No. 4-268316 (Patent Document 10) and JP-A No. 2002-253971 (PatentDocument 11), methods of forming a sulfonic acid-type cation-exchangeresin having a desired particle diameter, are disclosed. As stated, theparticle diameter of the sulfonic acid-type cation-exchange resin is animportant factor in obtaining a sufficient reaction conversion.

Various improvements on the structure of a resin product, which is thebase material of a sulfonic acid-type cation-exchange resin, have beenmade. The sulfonic acid-type cation-exchange resin is a resin obtainedby sulfonating a styrene-divinylbenzene copolymer which is obtained byradically copolymerizing styrene and divinylbenzene. The divinylbenzenein polymerization does not only prevent a polystyrene chain fromdissolving in an organic solvent, but the content thereof is also animportant factor in controlling the size of a pore (size of a gelmicropore) within the sulfonic acid-type cation-exchange resin formed bycapturing a polar solvent, or the mechanical strength of the sulfonicacid-type cation-exchange resin. In other words, a sulfonic acid-typecation-exchange resin with a low content of divinylbenzene has a highcatalytic activity due to a large gel micropore, but has a lowmechanical strength. In addition, if the content thereof is high, themechanical strength increases, but the gel micropore size decreases,which causes decreased activity.

In order to improve the diffusion within the particles, there areion-exchange resins in which the degree of crosslinking is increased asthe content of divinylbenzene is increased, that are formed with a largehole referred to as a ‘macroporous’ having a particle diameter of 20 nmor more within the particles by physical treatment. However, in the casewhere an ion-exchange resin having this macroporous adsorbs a moleculehaving high polarity, such as water, a crosslinked structure tends toinhibit the bulge of particles caused by the swelling, which eventuallycollapses when it can no longer endure the swelling. JP-A No. 5-97741(Patent Document 12) and JP-A No. 6-320009 (Patent Document 13) describea method which complements the respective defects by simultaneousfilling a sulfonic acid-type cation-exchange resin having a low contentof divinylbenzene and a sulfonic acid-type cation-exchange resin havinga high content of divinylbenzene into a reactor. Further, an improvementon a reaction conversion is reported in Nippon Steel Chemical Co., Ltd.WO 2000/00454 (Patent Document 14), which suggests a sulfonic acid-typecation-exchange resin having large gel micropores by using largemolecules such as divinylbiphenyl instead of divinylbenzene.

As such, various techniques related to catalysts have been investigated,particularly for the mercapto group-containing compound, and realizedthat apart from the ones which are easily available such asaminoethanethiol and pyridineethanethiol, its production processrequires many reaction and separation processes, and many of theoperations to obtain a product with high purity are complicated. In allcases, there is room for improvement in selectivity. The development ofa high selectivity catalyst is demanded. If the improvement inselectivity is attempted, it can not only reduce the load of performinga by-product recovery process in the production process, but it alsoreduces the material ratio of phenol/acetone without deteriorating theselectivity by increasing the reaction temperature and thus leads to areduction in cost related to the process for recovering excess phenol.If the activity is reduced in some extent, it can be covered byincreasing the size of the reactor, and thus-caused cost-up forproducing bisphenol is very small. Therefore, the development ofcatalyst which is easy to produce and exhibits high selectivity at anequivalent conversion is demanded.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a modified ion exchangeresin catalyst which exhibits a higher bisphenols selectivity than theconventional modified ion exchange resins in processes for producingbisphenols by reacting a phenolic compound with ketones, and a processfor producing bisphenols.

The present inventors have conducted extensive studies to solve theabove problems, and as a result, they have found that by using themodified acidic ion exchange resin in which at least one compoundselected from the group of compounds represented by the followingformulae:

(wherein, P is a phosphorous atom; S is a sulfur atom; H is a hydrogenatom; R1 is an alkylene or an alkenylene group having 1 to 6 carbonatom(s) which may have an alkyl group having 1 to 6 carbon atom(s), acycloalkyl group having 5 to 10 carbon atoms, an aryl group having 5 to10 carbon atoms, or a hydroxyl group as a substituent, and in which theone carbon may be replaced to a silicon atom and one moiety thereof mayhave a phenylene group; and each of R2, R3, and R4 independently is (1)an alkyl or an alkenyl group having 1 to 6 carbon atom(s) which may havea hydroxyl group or an aryl group having 5 to 10 carbon atoms as asubstituent, (2) a cycloalkyl group having 5 to 10 carbon atoms, or (3)an aryl group having 5 to 10 carbon atoms, and any one of R2, R3, and R4may be hydrogen); and

(wherein, P is a phosphorous atom; S is a sulfur atom; H is a hydrogenatom; R1 and R2 each is an alkylene or an alkenylene group having 1 to 6carbon atom(s) which may have an alkyl group having 1 to 6 carbonatom(s), a cycloalkyl group having 5 to 10 carbon atoms, an aryl grouphaving 5 to 10 carbon atoms, or a hydroxyl group as a substituent, andin which the one carbon may be replaced to a silicon atom and one moietymay have a phenylene group; and each of R3 and R4 independently is analkyl group having 1 to 6 carbon atom(s), a cycloalkyl group having 5 to10 carbon atoms, or an aryl group having 5 to 10 carbon atoms, and anyone of them may be hydrogen) is ionically bonded to an acidic functionalgroup of an acidic ion exchange resin, the selectivity of bisphenols isincreased, and as a result, bisphenols are obtained with highproductivity. Thus, they have completed the invention.

That is, the invention is an acidic ion exchange resin which is partlyneutralized by at least one compound selected from the group ofcompounds represented by the above (Formula 1) and (Formula 2), acatalyst for producing bisphenols formed with this ion exchange resin,and a process for producing bisphenols by using the catalyst.

BEST MODE FOR CARRYING OUT THE INVENTION

The ion exchange resin used for the invention is preferably an acidicion exchange resin, and examples include common type so called astrong-acid ion-exchange resin which is obtained by introducing asulfone group into a styrene-divinylbenzene copolymer, andperfluoroalkylsulfonic acid resins such as Nafion.

The modified ion exchange resin of the invention is obtained byionically bonding an acidic ion exchange resin with at least onecompound selected from compounds represented by (Formula 1) and (Formula2):

(wherein, P is a phosphorous atom; S is a sulfur atom; H is a hydrogenatom; R1 is an alkylene or an alkenylene group having 1 to 6 carbonatom(s) which may have an alkyl group having 1 to 6 carbon atom(s), acycloalkyl group having 5 to 10 carbon atoms, an aryl group having 5 to10 carbon atoms, or a hydroxyl group as a substituent, and in which theone carbon may be replaced to a silicon atom and one moiety thereof mayhave a phenylene group; and each of R2, R3, and R4 independently is (1)an alkyl or an alkenyl group having 1 to 6 carbon atom(s) which may havea hydroxyl group or an aryl group having 5 to 10 carbon atoms as asubstituent, (2) a cycloalkyl group having 5 to 10 carbon atoms, or (3)an aryl group having 5 to 10 carbon atoms, and any one of R2, R3, and R4may be hydrogen);

(wherein, P is a phosphorous atom; S is a sulfur atom; H is a hydrogenatom; R1 and R2 each is an alkylene or an alkenylene group having 1 to 6carbon atom(s) which may have an alkyl group having 1 to 6 carbonatom(s), a cycloalkyl group having 5 to 10 carbon atoms, an aryl grouphaving 5 to 10 carbon atoms, or a hydroxyl group as a substituent, andin which the one carbon may be replaced to a silicon atom and one moietymay have a phenylene group; and each of R3 and R4 independently is analkyl group having 1 to 6 carbon atom(s), a cycloalkyl group having 5 to10 carbon atoms, or an aryl group having 5 to 10 carbon atoms, and anyone of them may be hydrogen).

The modified ion exchange resin of the invention either uses thecompound selected from compounds represented by (Formula 1) and (Formula2) alone or in combination of plural kinds. The resin also may be partlyneutralized by a cation other than the compound represented by (Formula1), (Formula 2). Examples of the cation other than the compoundsrepresented by (Formula 1), (Formula 2), include cations of amines andammoniums, phosphoniums, phosphines, metal cations, and the like.

A preparation of the modified acidic ion exchange resin of the inventionis preferably that eventually just before the use in a reaction orduring the reaction, at least one cationic compound selected fromcompounds represented by (Formula 1) and (Formula 2) is ionically bondedto an acidic functional group of an acidic ion exchange resin, and theresin may be prepared by using the cationic compound and/or a precursorforming such state. For example, a neutrally charged compoundrepresented by (Formula 3), (Formula 4) may be contacted as theprecursor with an acidic ion exchange resin for cationization.

(wherein, P is a phosphorous atom; S is a sulfur atom; H is a hydrogenatom; R1 is an alkylene or an alkenylene group having 1 to 6 carbonatom(s) which may have an alkyl group having 1 to 6 carbon atom(s), acycloalkyl group having 5 to 10 carbon atoms, an aryl group having 5 to10 carbon atoms, or a hydroxyl group as a substituent, and in which theone carbon may be replaced to a silicon atom and one moiety thereof mayhave a phenylene group; and each of R2 and R3 independently is (1) analkyl or an alkenyl group having 1 to 6 carbon atom(s) which may have ahydroxyl group or an aryl group having 5 to 10 carbon atoms as asubstituent, (2) a cycloalkyl group having 5 to 10 carbon atoms, or (3)an aryl group having 5 to 10 carbon atoms)

(wherein, P is a phosphorous atom; S is a sulfur atom; H is a hydrogenatom; R1 and R2 each is an alkylene or an alkenylene group having 1 to 6carbon atom(s) which may have an alkyl group having 1 to 6 carbonatom(s), a cycloalkyl group having 5 to 10 carbon atoms, an aryl grouphaving 5 to 10 carbon atoms, or a hydroxyl group as a substituent, andin which the one carbon may be replaced to a silicon atom and one moietythereof may have a phenylene group; and R3 is (1) an alkyl or an alkenylgroup having 1 to 6 carbon atom(s) which may have a hydroxyl group or anaryl group having 5 to 10 carbon atoms as a substituent, (2) acycloalkyl group having 5 to 10 carbon atoms, or (3) an aryl grouphaving 5 to 10 carbon atoms)

Examples of the precursor for a mercapto group include thioethers,disulfides, and thioacetates, and these also may be used.

For the compound which is represented by (Formula 1) used for theinvention, each of P, S, and H in Formula 1 respectively is aphosphorous atom, a sulfur atom, and a hydrogen atom. R1 is an alkyleneor an alkenylene group having 1 to 6 carbon atom(s) which may have analkyl group having 1 to 6 carbon atom(s), a cycloalkyl group having 5 to10 carbon atoms, an aryl group having 5 to 10 carbon atoms, or ahydroxyl group as a substituent, and in which the one carbon may bereplaced to a silicon atom, one moiety thereof may have a phenylenegroup, and the phenylene group may be at the terminal of R1. Each of R2,R3, and R4 independently is any one of (1) an alkyl or an alkenyl grouphaving 1 to 6 carbon atom(s) which may have a hydroxyl group or an arylgroup having 5 to 10 carbon atoms as a substituent, (2) a cycloalkylgroup having 5 to 10 carbon atoms, and (3) an aryl group having 5 to 10carbon atoms, and any one of R2, R3, and R4 may be hydrogen.

A compound relatively easy to be synthesized among the compoundsrepresented by (Formula 1) is a compound in which in Formula 1, R1 is analkylene group having 1 to 6 carbon atom(s) which may have an alkylgroup having 1 to 6 carbon atom(s), a cycloalkyl group having 5 to 10carbon atoms, an aryl group having 5 to 10 carbon atoms, or a hydroxylgroup as a substituent, and one moiety thereof may have a phenylenegroup; and each of R2, R3, and R4 independently is any one of (1) analkyl group having 1 to 6 carbon atom(s) which may have a hydroxyl groupor an aryl group having 5 to 10 carbon atoms as a substituent and (2) anaryl group having 5 to 10 carbon atoms, and any one of R2, R3, and R4may be hydrogen.

A more preferable compound among the compounds represented by(Formula 1) is a compound in which in Formula 1, R1 is an alkylene grouphaving 3 to 6 carbon atoms which may have an alkyl group having 1 to 6carbon atom(s), a cycloalkyl group having 5 to 10 carbon atoms, an arylgroup having 5 to 10 carbon atoms, or a hydroxyl group as a substituent,and one moiety thereof may have a phenylene group; and each of R2, R3,and R4 independently is any one of (1) an alkyl group having 1 to 6carbon atom(s) which may have a hydroxyl group or an aryl group having 5to 10 carbon atoms as a substituent and (2) an aryl group having 5 to 10carbon atoms, and any of R2, R3, and R4 may be hydrogen.

Examples of R1 having a phenylene group on its one moiety among thosecompounds represented by (Formula 1) include —CH2-C6H4-CH2-,—C6H4-CH(CH3)-, —C6H4-CH2-CH2-, and the like, but others may also beincluded.

For the compound which is represented by (Formula 2) used for theinvention, each of P, S, and H in Formula 2 respectively is aphosphorous atom, a sulfur atom, and a hydrogen atom. R1 and R2 each isan alkylene or an alkenylene group having 1 to 6 carbon atom(s) whichmay have an alkyl group having 1 to 6 carbon atom(s), a cycloalkyl grouphaving 5 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms,or a hydroxyl group as a substituent, and in which the one carbon may bereplaced to a silicon atom and one moiety thereof may have a phenylenegroup; Each of R3 and R4 independently is any one of an alkyl grouphaving 1 to 6 carbon atom(s), a cycloalkyl group having 5 to 10 carbonatoms, and an aryl group having 5 to 10 carbon atoms, and any one ofthem may be hydrogen.

A compound relatively easy to be synthesized among the compoundsrepresented by (Formula 2) is a compound in which in (Formula 2), R1 andR2 each is an alkylene group having 1 to 6 carbon atom(s) which may havean alkyl group having 1 to 6 carbon atom(s), a cycloalkyl group having 5to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms, or ahydroxyl group as a substituent, and one moiety thereof may have aphenylene group; and each of R3 and R4 independently is any one of (1)an alkyl group having 1 to 6 carbon atom(s) which may have a hydroxylgroup or an aryl group having 5 to 10 carbon atoms as a substituent and(2) an aryl group having 5 to 10 carbon atoms, and any one of R3 and R4may be hydrogen.

Examples of R1 and R2 each having a phenylene group on its one moietyamong those compounds represented by (Formula 2) include —CH2-C6H4-CH2-,—C6H4-CH(CH3)-, —C6H4-CH2-CH2-, and the like, but others may also beincluded.

A modification method is not particularly limited. Examples of easymethod include contacting in the liquid phase by dissolving in asolution such as water or an organic solvent, and contacting with an ionexchange resin in the gas phase when using a volatile substance.

Examples of the conventionally known method include a method disclosedin JP-B No. 46-19953 and the like. In addition, the compound representedby (Formula 1) can be obtained by reacting a raw material capable ofderiving the compound represented by (Formula 1) in the ion exchangeresin. Further, a method which eventually forms a modified acidic ionexchange resin may be used such as a method neutralizing an ion exchangeresin by using an equivalent or excess amount of cationic compound orprecursor thereof, and then partially returning to an acid-type bycontacting the ion exchange resin with an acidic solution.

The modified amount of modified acidic ion exchange resin catalyst inthe invention is preferably 0.1 to 50% of total sulfonic acid group.Thereby, it is possible to exhibit the modification effect to a maximumextent without causing the decrease in the activity due to the decreasein an amount of acid.

The method of measuring the amount of acid of the ion exchange resin isnot particularly limited, but can be determined by a general method ofmeasuring the exchange content of an acidic ion exchange resin. In theinvention, the amount is determined from a titration curve obtained bystirring 0.2 g of a dry resin in 200 ml of a 10% aqueous NaCl solutionfor one hour and titrating the whole amount of the filtrate with a 0.05N aqueous NaOH solution.

In the invention, for phenol to be used as a raw material for producingbisphenol A, a generally available industrial phenol can be used. Theindustrial phenol includes one prepared by a cumene method, a tolueneoxidation method, or the like, and any of which maybe used. Generally,phenol having a purity of 98% or more is commercially available. Suchthe industrial phenol maybe used as it is in the synthesis reaction ofbisphenol A, but preferably phenol which is preliminarily treated with astrong acid-type cation-exchange resin in a continuous or batch modebefore carrying out the reaction at a treatment temperature of 50 to120° C. during a contact time of 5 minutes to 10 hours and polymerizedwith a carbonyl compound derived from acetone, is used. Even morepreferably, one obtained by the process wherein the industrial phenol isbrought into contact with a strong acid-type cation-exchange resin asdescribed above and is then subjected to a distillation treatment underthe condition of a normal pressure to a reduced pressure of 10 mmHg, ata temperature of 70 to 200° C., is used.

Acetone used in the invention is not particularly limited, but it may bea commercially available industrial acetone. Generally, acetone having apurity of 99% or more is available.

The amounts (quantitative ratios) of phenol and acetone, used as rawmaterials, to be used, are not particularly limited, but the molar ratioof phenol/acetone is recommended to be preferably in the range of 0.1 to100, and more preferably in the range of 0.5 to 50. If the amount ofphenol is too small, it is difficult to accomplish a high conversion ofacetone as a raw material, if the amount of phenol is too large, thereactor becomes unreasonably larger because phenol is used as the higheramount than required, and moreover, massive circulation of phenol isalso required, even though a high conversion of acetone can beaccomplished. Thus, efficient production cannot be accomplished.

As disclosed in EP No. 583712, the mixture of those raw materials maypreliminarily contain 1 or less % of water.

In the invention, the reaction temperature is not particularly limited,but it is preferably in the range of 0 to 300° C., and more preferablyin the range of 30 to 200° C. If the reaction temperature is extremelylow, the reaction rate decreases and thus the productivity of a reactionproduct also decreases. On the other hand, if the reaction temperatureis extremely high, an undesirable side reaction, or the like proceeds,thus leading to the increase in the amount of by-products. Theexcessively high reaction temperature is unfavorable for stability ofphenol and acetone as raw materials and further bisphenol A as aproduct, decreases the reaction selectivity, and is not economical.Therefore, it is not economical.

The reaction can be carried out under any of a reduced pressure, anapplied pressure, and a normal pressure. From the viewpoint of thereaction efficiency (reaction efficiency per unit volume), it is notpreferable to carry out the reaction under too low of pressure. Usually,the pressure for carrying out the reaction is preferably in the range of0.01 to 20 MPa, and more preferably in the range of 0.05 to 10 MPa. Ofcourse, the invention is not limited to such pressure ranges.

In addition, when carrying out the invention, the amount of the catalystto be used is not particularly limited, but for example, when carryingout the reaction in a batch mode, it is recommended to carry out theinvention preferably in the range of 0.001 to 200% by weight, and morepreferably in the range of 0.1 to 50% by weight with respect to phenolas a raw material.

When carrying out the invention, it is possible to carry out thereaction in the diluted state by adding a solvent or gas which is inertto the catalyst and the reaction reagent in the reaction system.Specifically, aliphatic hydrocarbons such as methane, ethane, propane,butane, hexane, and cyclohexane, and an inert gas such as nitrogen,argon, and helium, and if necessary, hydrogen can be used as diluents.

When carrying out the invention, the method can be carried out in any ofa batch, semi-batch, or continuous flow system. It can be carried out inany of a liquid phase, a gas phase, and a gas-liquid mixed phase.Preferably, from the viewpoint of the reaction efficiency, it isrecommended that the reaction is carried out in the liquid phase. For amethod for charging a catalyst, various kinds of methods using, forexample, a fixed bed, a fluidized bed, a suspended bed, and a platefixed bed can be employed, and any of which can be used.

The reaction time (retention time or catalytic contact time in the flowsystem) is not particularly limited, but it is usually 0.1 second to 30hours, and preferably 0.5 second to 15 hours. After the reaction, thereaction product can be separated and recovered from the catalysts, orthe like, by a separation method such as filtration, extraction, anddistilling-off. Bisphenol A as a desired product can be separated,purified from the recovered compound by performing a sequentialtreatment of solvent extraction, distillation, alkali treatment, acidtreatment and the like or an ordinary separation and purification methodsuitably combining them, and obtained. In addition, unreacted rawmaterials can be recovered and recycled into the reaction system foruse.

In the case of a batch reaction, the catalyst which is separated andrecovered from the reaction product after the reaction, can be used asit is, or partially or wholly reproduced to be repeatedly used for thereaction. In the case of carrying out the reaction in a fixed bed or afluidized bed flow reaction system, if the catalyst is provided to thereaction and thereby a part or all of the catalysts is inactivated or islowered in the activity, the reaction is interrupted, and thereafter thecatalyst can be reproduced and then provided to the reaction.Alternatively, a part of the catalyst can be withdrawn continuously orintermittently and reproduced, and then recycled to the reactor forre-use. Further, a fresh catalyst can be intermittently supplied to thereactor. When carrying out the reaction in a moving-bed flow reaction,the catalyst can be separated, recovered and, if necessary, reproduced,as in the batch reaction.

A catalyst can be reproduced by using any method as long as itscatalytic ability is recovered, and for example the catalyst may bewashed with water or an organic solvent, or may be subjected to are-modification after being washed with an acidic solvent. In addition,the catalyst may be modified after being washed alternately with anacidic solvent and a basic solvent several times and finally with anacidic solvent.

EXAMPLES

Hereinafter, the present invention will be described in more detail withreference to Examples. However, the invention is not intended to belimited to Examples.

Herein, although an ion exchange resin of same brand is used, sincethere may be a case where its catalytic ability differs in a BPAsynthesis reaction as its lot differs, Amberlyst 31 of same brand andsame lot is used in all Examples and Comparative Examples below.

Example 1 (1) Synthesis of (3-mercaptopropyl)triphenylphosphoniumbromide

14.0 g of (3-mercaptopropyl)triphenylphosphoniumbromide and 2.35 g ofthiourea were dissolved in 335 ml of ethanol, and the mixture wasrefluxed for about 16 hours. The resultant solution was ice-cooled,filtered, and thus-obtained solid was sufficiently dried to obtain WhiteCrystal 1. 5.3 g of White Crystal 1 was dissolved in 100 ml ofthoroughly deaerated ion-exchange water, and thereto an aqueous solutionprepared by dissolving 0.5 g of sodium hydroxide to 25 ml ofion-exchange water was added dropwise for 30 minutes under a nitrogenatmosphere. Thereafter, the mixture was stirred at 60° C. for 2 hoursand cooled, under a nitrogen atmosphere. The solid obtained byfiltration was washed with ion-exchange water, further dissolved inchloroform, and repeatedly, subjected washing with ion-exchange waterand a separation. The chloroform phase was desolvated, and thus obtainedsolid was recrystallized from chloroform and dried to obtain WhiteCrystal 2. When White Crystal 2 was analyzed with ¹H-NMR and FD-MSmeasurements, it was confirmed to have a structure of Formula 5.

(2) Preparation of (3-mercaptopropyl)triphenylphosphonium modified ionexchange resin catalyst

3 g of thoroughly washed and dried Amberlyst 31 was stirred vigorouslyin 60 ml of 50% aqueous acetonitrile solution. Thereto, 30 ml of 0.077mol/L (3-mercaptopropyl)triphenylphosphoniumbromide-50% aqueousacetonitrile solution which is prepared by using White Crystal 2obtained from (1) was slowly added dropwise. After the dropwiseaddition, the mixture was subsequently stirred for 5 hours, and thenrepeatedly subjected to a filtration and washing with ion-exchangewater. Thereafter, the resultant was vacuum dried at 80° C. at least 10hours to obtain Catalyst 1. The amount of acid of the catalyst in adry-state was 3.47 milliequivalents/g.

(3) Bisphenol A synthesis reaction

To a 70 ml pressure-resistant reactor, 0.35 g of Catalyst 1 prepared in(2), 6.63 g of phenol, and 0.37 g of acetone were charged, and thereactor was pressurized with nitrogen gas under 0.5 MPa of a gaugepressure, and then the reaction was conducted with heating and stirringat 75° C. for 2 hours. Thereafter, the resultant was cooled to roomtemperature. After the pressure discharge, the reaction solution wastaken out, and analytically quantified by a liquid chromatographymethod. As a result, the conversion of acetone was 88.1% and theselectivity of pp′-bisphenol A was 94.1%.

Example 2 (1) Synthesis of (4-mercaptobutyl)triphenylphosphoniumbromide

11.0 g of (4-bromobutyl)triphenylphosphoniumbromide and 1.75 g ofthiourea were dissolved in 250 ml of ethanol, and the mixture wasrefluxed for about 16 hours. About 170 ml of ethanol was distilled-offtherefrom, further the reaction solution was cooled to not more than 0°C., and then left over for a filtration. Thus-obtained solid wassufficiently washed with chloroform and dried to obtain White Crystal 3.6.0 g of White Crystal 3 was dissolved in 140 ml of thoroughly deaeratedion-exchange water, and thereto 30 ml of 1.6% aqueous sodium hydroxidesolution was added dropwise under a nitrogen atmosphere. Thereafter, themixture was stirred under a nitrogen atmosphere at 60° C. for 2 hours,and cooled. Thereto, a 12 ml of 5.6% aqueous HBr solution was added.Thereto, 70 ml of chloroform was added, well mixed, and then the waterphase and chloroform phase were separated. The chloroform phase wasdesolvated to obtain White Crystal 4. When White Crystal 4 was analyzedwith ¹H-NMR and LC-MS measurements, it was confirmed to have a structureof Formula 6.

(2) Preparation of (4-mercaptobutyl)triphenylphosphonium modified ionexchange resin catalyst

3 g of thoroughly washed and dried Amberlyst 31 was stirred vigorouslyin 60 ml of ion-exchange water. Thereto, 196 ml of 0.0116 mol/L(4-mercaptobutyl)triphenylphosphoniumbromide-aqueous solution which isprepared by using White Crystal 4 obtained from (1) was slowly addeddropwise. After the dropwise addition, the mixture was subsequentlystirred for 5 hours, and then repeatedly subjected to a filtration andwashing with ion-exchange water. Thereafter, the resultant was vacuumdried at 80° C. for at least 10 hours to obtain Catalyst 2. The amountof acid of the catalyst in a dry-state was 3.49 milliequivalents/g.

(3) Bisphenol A synthesis reaction

To a 70 ml pressure-resistant reactor, 0.35 g of Catalyst 2 prepared in(2), 6.63 g of phenol, and 0.37 g of acetone were charged, and thereactor was pressurized with nitrogen gas under 0.5 MPa of a gaugepressure, and then the reaction was conducted with heating and stirringat 75° C. for 2 hours. Thereafter, the resultant was cooled to roomtemperature. After the pressure discharge, the reaction solution wastaken out, and analytically quantified by a liquid chromatographymethod. As a result, the conversion of acetone was 94.9% andtheselectivity of pp′-bisphenol A was 93.9%.

Example 3 (1) Synthesis of (5-mercaptopentyl)triphenylphosphoniumbromide

20.7 g of 1,5-dibromopentane and 23.6 g of triphenylphosphin weredissolved in 55 ml of toluene, and the mixture was stirred at about 60°C. for 18 hours. Thereafter, supernatant toluene was removed, theresidual was dissolved in ion-exchange water, and the resultant aqueoussolution was repeatedly extruded using toluene. Next, the aqueoussolution was mixed by adding chloroform, separated, and obtainedchloroform phase was repeatedly extruded by using ion-exchange water andthe chloroform phase was desolvated, to obtain White Crystal 5. 7.0 g ofWhite Crystal 5 and 1.1 g of thiourea were dissolved in 150 ml ofethanol, and the mixture was refluxed for about 16 hours. Ethanol wasdistilled-off from the solution, and then dried to obtain White Crystal6. 3.0 g of White Crystal 6 was dissolved in 75 ml of thoroughlydeaerated ion-exchange water, and thereto 17 ml of 1.6% aqueous sodiumhydroxide solution was added dropwise under a nitrogen atmosphere.Thereafter, the mixture was stirred under a nitrogen atmosphere at 60°C. for 2 hours, and cooled. Thereto, a 8 ml of 5.6% aqueous HBr solutionwas added. Thereto, 30 ml of chloroform was added, well mixed, and thenthe water phase and chloroform phase were separated. The chloroformphase was desolvated to obtain White Crystal 7. When White Crystal 7 wasanalyzed with ¹H-NMR and LC-MS measurements, it was confirmed to have astructure of Formula 7.

(2) Preparation of (5-mercaptopentyl)triphenylphosphonium modified ionexchange resin catalyst

3 g of thoroughly washed and dried Amberlyst 31 was stirred vigorouslyin 60 ml of ion-exchange water. Thereto, 55 ml of 0.042 mol/L(5-mercaptopentyl)triphenylphosphoniumbromide-aqueous solution which isprepared by using White Crystal 7 obtained from (1) was slowly addeddropwise. After the dropwise addition, the mixture was subsequentlystirred for 5 hours, and then repeatedly subjected to a filtration andwashing with ion-exchange water. Thereafter, the resultant was vacuumdried at 80° C. at least 10 hours to obtain Catalyst 3. The amount ofacid of the catalyst in a dry-state was 3.43 milliequivalents/g.

(3) Bisphenol A synthesis reaction

To a 70 ml pressure-resistant reactor, 0.35 g of Catalyst 3 prepared in(2), 6.63 g of phenol, and 0.37 g of acetone were charged, and thereactor was pressurized with nitrogen gas under 0.5 MPa of a gaugepressure, and then the reaction was conducted with heating and stirringat 75° C. for 2 hours. Thereafter, the resultant was cooled to roomtemperature. After the pressure discharge, the reaction solution wastaken out, and analytically quantified by a liquid chromatographymethod. As a result, the conversion of acetone was 94.9% and theselectivity of pp′-bisphenol A was 94.0%.

Example 4 (1) Synthesis of (6-mercaptohexyl)triphenylphosphoniumbromide

23.4 g of 1,6-dibromohexane and 25.0 g of triphenylphosphin weredissolved in 35 ml of toluene, and the mixture was stirred at about 60°C. for 18 hours. Thereafter, supernatant toluene was removed, theresidual was dissolved in ion-exchange water, and the resultant aqueoussolution was repeatedly extruded using toluene. Next, the aqueoussolution was mixed by adding chloroform, separated, and obtainedchloroform phase was repeatedly extruded by using ion-exchange water andthe chloroform phase was desolvated, to obtain White Crystal 8. 7.2 g ofWhite Crystal 8 and 1.1 g of thiourea were dissolved in 150 ml ofethanol, and the mixture was refluxed for about 16 hours. Ethanol wasdistilled-off from the solution, and then dried to obtain White Crystal9. 3.1 g of White Crystal 9 was dissolved in 75 ml of thoroughlydeaerated ion-exchange water, and thereto 17 ml of 1.6% aqueous sodiumhydroxide solution was added dropwise under a nitrogen atmosphere.Thereafter, the mixture was stirred under a nitrogen atmosphere at 60°C. for 2 hours, and cooled. Thereto, a 8 ml of 5.6% aqueous HBr solutionwas added. Thereto, 30 ml of chloroform was added, well mixed, and thenthe water phase and chloroform phase were separated. The chloroformphase was desolvated to obtain White Crystal 10. When White Crystal 10was analyzed with ¹H-NMR and LC-MS measurements, it was confirmed tohave a structure of Formula 8.

(2) Preparation of (6-mercaptohexyl)triphenylphosphonium modified ionexchange resin catalyst

3 g of thoroughly washed and dried Amberlyst 31 was stirred vigorouslyin 60 ml of ion-exchange water. Thereto, 55 ml of 0.042 mol/L(6-mercaptohexyl)triphenylphosphoniumbromide-aqueous solution which isprepared by using White Crystal 10 obtained from (1) was slowly addeddropwise. After the dropwise addition, the mixture was subsequentlystirred for 5 hours, and then repeatedly subjected to a filtration andwashing with ion-exchange water. Thereafter, the resultant was vacuumdried at 80° C. for at least 10 hours to obtain Catalyst 4. The amountof acid of the catalyst in a dry-state was 3.41 milliequivalents/g.

(3) Bisphenol A synthesis reaction

To a 70 ml pressure-resistant reactor, 0.35 g of Catalyst 4 prepared in(2), 6.63 g of phenol, and 0.37 g of acetone were charged, and thereactor was pressurized with nitrogen gas under 0.5 MPa of a gaugepressure, and then the reaction was conducted with heating and stirringat 75° C. for 2 hours. Thereafter, the resultant was cooled to roomtemperature. After the pressure discharge, the reaction solution wastaken out, and analytically quantified by a liquid chromatographymethod. As a result, the conversion of acetone was 95.1% and theselectivity of pp′-bisphenol A was 94.1%.

Example 5 (1) Synthesis of(4-mercaptobutyl)diphenyl(p-tolyl)phosphoniumbromide

15.3 g of 1,4-dibromobutane and 19.2 g of diphenyl(p-tolyl)phosphin weredissolved in 40 ml of toluene, and the mixture was stirred under anitrogen atmosphere at about 70° C. for 16 hours. The resultant solutionwas cooled, filtered, and thus-obtained solid was washed with tolueneand dried to obtain White Crystal 11. 10 g of White Crystal 11 and 1.55g of thiourea were dissolved in 250 ml of ethanol, and the mixture wasrefluxed for about 16 hours. Ethanol was distilled-off from thesolution, and thus-obtained solid was washed with ethanol and dried toobtain White Crystal 12. 6.0 g of White Crystal 12 was dissolved in 140ml of thoroughly deaerated ion-exchange water, and thereto 31 ml of 1.6%aqueous sodium hydroxide solution was added dropwise under a nitrogenatmosphere. Thereafter, the mixture was stirred under a nitrogenatmosphere at 60° C. for 2 hours, and cooled. Thereto, a 13 ml of 5.6%aqueous HBr solution was added. Thereto, 70 ml of chloroform was added,well mixed, and then the water phase and chloroform phase wereseparated. The chloroform phase was desolvated to obtain White Crystal13. When White Crystal 13 was analyzed with ¹H-NMR and LC-MSmeasurements, it was confirmed to have a structure of Formula 9.

(2) Preparation of (4-mercaptobutyl)diphenyl(p-tolyl)phosphoniummodified ion exchange resin catalyst

3 g of thoroughly washed and dried Amberlyst 31 was stirred vigorouslyin 60 ml of ion-exchange water. Thereto, 196 ml of 0.0116 mol/L(4-mercaptobutyl)diphenyl(p-tolyl)phosphoniumbromide-aqueous solutionwhich is prepared by using White Crystal 13 obtained from (1) was slowlyadded dropwise. After the dropwise addition, the mixture wassubsequently stirred for 5 hours, and then repeatedly subjected to afiltration and washing with ion-exchange water. Thereafter, theresultant was vacuum dried at 80° C. for at least 10 hours to obtainCatalyst 5. The amount of acid of the catalyst in a dry-state was 3.43milliequivalents/g.

(3) Bisphenol A synthesis reaction

To a 70 ml pressure-resistant reactor, 0.35 g of Catalyst 5 prepared in(2), 6.63 g of phenol, and 0.37 g of acetone were charged, and thereactor was pressurized with nitrogen gas under 0.5 MPa of a gaugepressure, and then the reaction was conducted with heating and stirringat 75° C. for 2 hours. Thereafter, the resultant was cooled to roomtemperature. After the pressure discharge, the reaction solution wastaken out, and analytically quantified by a liquid chromatographymethod. As a result, the conversion of acetone was 93.3% and theselectivity of pp′-bisphenol A was 93.8%.

Example 6 (1) Synthesis of(4-mercaptomethylbenzyl)triphenylphosphoniumbromide

6.3 g of 1,4-bis(bromomethyl)benzene and 6.5 g of triphenylphosphin weredissolved in 60 ml of toluene, and the mixture was stirred under anitrogen atmosphere at about 60° C. for 3 hours. The resultant solutionwas cooled, filtered, and thus-obtained solid was washed with tolueneand dried to obtain White Crystal 14. 10 g of White Crystal 14 and 1.5 gof thiourea were dissolved in 100 ml of ethanol, and the mixture wasrefluxed for about 2 hours. Ethanol was distilled-off from the solution,and thus-obtained solid was dried to obtain White Crystal 15. 11.0 g ofWhite Crystal 15 was dissolved in 300 ml of thoroughly deaeratedion-exchange water, and thereto 15 ml of 5.4% aqueous sodium hydroxidesolution was added dropwise under a nitrogen atmosphere. Thereafter, themixture was stirred under a nitrogen atmosphere at 60° C. for 3 hours,and cooled. Thereto, a 7.8 ml of 5.3% aqueous HBr solution was added.After being stirred for several minutes, the mixture was left to settle,the water phase was taken out and cooled, and left as it is for another16 hours to settle. The resultant was filtered, and thus-obtained solidwas washed with cold water and dried to obtain White Crystal 16. WhenWhite Crystal 16 was analyzed with ¹H-NMR and LC-MS measurements, it wasconfirmed to have a structure of Formula 10.

(2) Preparation of (4-mercaptomethylbenzyl)triphenylphosphonium modifiedion exchange resin catalyst

3 g of thoroughly washed and dried Amberlyst 31 was stirred vigorouslyin 60 ml of 25% aqueous acetonitrile solution. Thereto, 120 ml of 0.0188mol/L (4-mercaptomethylbenzyl)triphenylphosphoniumbromide-25% aqueousacetonitrile solution which is prepared by using White Crystal 16obtained from (1) was slowly added dropwise. After the dropwiseaddition, the mixture was subsequently stirred for 5 hours, and thenrepeatedly subjected to a filtration and washing with ion-exchangewater. Thereafter, the resultant was vacuum dried at 80° C. for at least10 hours to obtain Catalyst 6. The amount of acid of the catalyst in adry-state was 3.40 milliequivalents/g.

(3) Bisphenol A synthesis reaction

To a 70 ml pressure-resistant reactor, 0.35 g of Catalyst 6 prepared in(2), 6.63 g of phenol, and 0.37 g of acetone were charged, and thereactor was pressurized with nitrogen gas under 0.5 MPa of a gaugepressure, and then the reaction was conducted with heating and stirringat 75° C. for 2 hours. Thereafter, the resultant was cooled to roomtemperature. After the pressure discharge, the reaction solution wastaken out, and analytically quantified by a liquid chromatographymethod. As a result, the conversion of acetone was 93.9% and theselectivity of pp′-bisphenol A was 94.0%.

Example 7 (1) Synthesis of(4-mercaptomethylbenzyl)diphenylpropylphosphoniumbromide

6.3 g of 1,4-bis(bromomethyl)benzene and 5.4 g of diphenylpropylphosphinwere dissolved in 60 ml of toluene, and the mixture was stirred under anitrogen atmosphere at about 60° C. for 5 hours. The resultant solutionwas cooled, filtered, and thus-obtained solid was washed with tolueneand dried to obtain White Crystal 17. 10 g of White Crystal 17 and 1.53g of thiourea were dissolved in 100 ml of ethanol, and the mixture wasrefluxed for about 3 hours. Ethanol was distilled-off from the solution,and thus-obtained solid was dried to obtain White Crystal 18. 11.0 g ofWhite Crystal 18 was dissolved in 300 ml of thoroughly deaeratedion-exchange water, and thereto 15 ml of 5.4% aqueous sodium hydroxidesolution was added dropwise under a nitrogen atmosphere. Thereafter, themixture was stirred under a nitrogen atmosphere at 60° C. for 3 hours,and cooled. Thereto, a 7.8 ml of 5.3% aqueous HBr solution was added.After being stirred for several minutes, the mixture was left to settle,the water phase was taken out and cooled, and left as it is for another16 hours to settle. The resultant was filtered, and thus-obtained solidwas washed with cold water and dried to obtain White Crystal 19. WhenWhite Crystal 19 was analyzed with ¹H-NMR and LC-MS measurements, it wasconfirmed to have a structure of Formula 11.

(2) Preparation of (4-mercaptomethylbenzyl)diphenylpropylphosphoniummodified ion exchange resin catalyst

3 g of thoroughly washed and dried Amberlyst 31 was stirred vigorouslyin 60 ml of 25% aqueous acetonitrile solution. Thereto, 120 ml of 0.0188mol/L (4-mercaptomethylbenzyl)triphenylphosphoniumbromide-25% aqueousacetonitrile solution which is prepared by using White Crystal 19obtained from (1) was slowly added dropwise. After the dropwiseaddition, the mixture was subsequently stirred for 5 hours, and thenrepeatedly subjected to a filtration and washing with ion-exchangewater. Thereafter, the resultant was vacuum dried at 80° C. for at least10 hours to obtain Catalyst 7. The amount of acid of the catalyst in adry-state was 3.43 milliequivalents/g.

(3) Bisphenol A synthesis reaction

To a 70 ml pressure-resistant reactor, 0.35 g of Catalyst 7 prepared in(2), 6.63 g of phenol, and 0.37 g of acetone were charged, and thereactor was pressurized with nitrogen gas under 0.5 MPa of a gaugepressure, and then the reaction was conducted with heating and stirringat 75° C. for 2 hours. Thereafter, the resultant was cooled to roomtemperature. After the pressure discharge, the reaction solution wastaken out, and analytically quantified by a liquid chromatographymethod. As a result, the conversion of acetone was 94.8% and theselectivity of pp′-bisphenol A was 94.1%.

Comparative Example 1

While stirring 3 g of thoroughly washed and dried Amberlyst 31 in 60 mlof ion-exchange water, 30 ml of 0.077 mol/L aminoethanethiolhydrochloride aqueous solution was slowly added dropwise thereto. Afterthe dropwise addition, the mixture was subsequently stirred for 5 hours,and then repeatedly subjected to a filtration and washing withion-exchange water. Thereafter, the resultant was vacuum dried at 80° C.for at least 10 hours to obtain Catalyst 2. The amount of acid of thecatalyst in a dry-state was 4.14 milliequivalents/g.

To a 70 ml pressure-resistant reactor, 0.35 g of Catalyst 2, 6.63 g ofphenol, and 0.37 g of acetone were charged, and the reactor waspressurized with nitrogen gas under 0.5 MPa of a gauge pressure, andthen the reaction was conducted with heating and stirring at 75° C. for2 hours. Thereafter, the resultant was cooled to room temperature. Afterthe pressure discharge, the reaction solution was taken out, andanalytically quantified by a liquid chromatography method. As a result,the conversion of acetone was 84.9% and the selectivity of pp′-bisphenolA was 91.5%.

Comparative Example 2

While stirring 3 g of thoroughly washed and dried Amberlyst 31 in 60 mlof ion-exchange water, 30 ml of 0.077 mol/L 4-pyridineethanethiolhydrochloride aqueous solution was slowly added dropwise thereto. Afterthe dropwise addition, the mixture was subsequently stirred for 5 hours,and then repeatedly subjected to a filtration and washing withion-exchange water. Thereafter, the resultant was vacuum dried at 80° C.for at least 10 hours to obtain Catalyst 3. The amount of acid of thecatalyst in a dry-state was 3.94 milliequivalents/g.

To a 70 ml pressure-resistant reactor, 0.35 g of Catalyst 3, 6.63 g ofphenol, and 0.37 g of acetone were charged, and the reactor waspressurized with nitrogen gas under 0.5 MPa of a gauge pressure, andthen the reaction was conducted with heating and stirring at 75° C. for2 hours. Thereafter, the resultant was cooled to room temperature. Afterthe pressure discharge, the reaction solution was taken out, andanalytically quantified by a liquid chromatography method. As a result,the conversion of acetone was 94.0% and the selectivity of pp′-bisphenolA was 91.6%.

INDUSTRIAL APPLICABILITY

According to the present invention, it is possible to produce bisphenolswith good yield and selectivity, and to produce bisphenols withremarkably excellent safety, process, and cost.

1. A modified ion exchange resin, wherein at least one compound selectedfrom (A) and (B) shown below is ionically bonded to an acidic functionalgroup of an acidic ion exchange resin, (A) Compound represented byFormula 1:

(wherein, P is a phosphorous atom; S is a sulfur atom; H is a hydrogenatom; R1 is an alkylene or an alkenylene group having 1 to 6 carbonatom(s) which may have an alkyl group having 1 to 6 carbon atom(s), acycloalkyl group having 5 to 10 carbon atoms, an aryl group having 5 to10 carbon atoms, or a hydroxyl group as a substituent, and in which theone carbon may be replaced to a silicon atom and one moiety thereof mayhave a phenylene group; and each of R2, R3, and R4 independently is (1)an alkyl or an alkenyl group having 1 to 6 carbon atom(s) which may havea hydroxyl group or an aryl group having 5 to 10 carbon atoms as asubstituent, (2) a cycloalkyl group having 5 to 10 carbon atoms, or (3)an aryl group having 5 to 10 carbon atoms, and any one of R2, R3, and R4may be hydrogen); and (B) Compound represented by Formula 2:

(wherein, P is a phosphorous atom; S is a sulfur atom; H is a hydrogenatom; R1 and R2 each is an alkylene or an alkenylene group having 1 to 6carbon atom(s) which may have an alkyl group having 1 to 6 carbonatom(s), a cycloalkyl group having 5 to 10 carbon atoms, an aryl grouphaving 5 to 10 carbon atoms, or a hydroxyl group as a substituent, andin which the one carbon may be replaced to a silicon atom and one moietythereof may have a phenylene group; and each of R3 and R4 independentlyis an alkyl group having 1 to 6 carbon atom(s), a cycloalkyl grouphaving 5 to 10 carbon atoms, or an aryl group having 5 to 10 carbonatoms, and any one of them may be hydrogen).
 2. The modified ionexchange resin according to claim 1, wherein in the compound representedby the above Formula 1, R1 is an alkylene group having 1 to 6 carbonatom(s) which may have an alkyl group having 1 to 6 carbon atom(s), acycloalkyl group having 5 to 10 carbon atoms, an aryl group having 5 to10 carbon atoms, or a hydroxyl group as a substituent, and one moietythereof may have a phenylene group; and each of R2, R3, and R4independently is (1) an alkyl group having 1 to 6 carbon atom(s) whichmay have a hydroxyl group or an aryl group having 5 to 10 carbon atomsas a substituent or (2) an aryl group having 5 to 10 carbon atoms, andany one of R2, R3, and R4 may be hydrogen.
 3. The modified acidic ionexchange resin according to claim 1, wherein the compound represented bythe above Formula 1 is at least one compound represented by thefollowing Formula 3:

(wherein, P is a phosphorous atom; S is a sulfur atom; H is a hydrogenatom; and n is an integer, of 1 to 4).
 4. The modified acidic ionexchange resin according to claim 1 or 2, wherein the compound isionically bonded to 0.1 to 50 mol % of total acidic functional groupexisting in the acidic ion exchange resin.
 5. The modified acidic ionexchange resin according to claim 1, wherein the acidic ion exchangeresin is obtained by introducing a sulfone group into a styrene polymerand/or a styrene-divinylbenzene copolymer.
 6. A catalyst for producingbisphenols formed with the ion acidic exchange resin of claim
 1. 7. Aprocess for producing bisphenols comprising reacting a phenolic compoundwith ketones and/or aldehydes by using the modified acidic ion exchangeresin of claim 1 as a catalyst.
 8. The process for producing bisphenolsaccording to claim 6, wherein the phenolic compound is phenol and theketones is acetone.
 9. A Process for producing mercaptoalkylphosphosphonium compounds comprising reacting a halogenoalkyl phophoniumcompound and thiourea to prepare a isothiuronium salt, and thenproducing a mercapto alkylphosphonium compound from the isothiuroniumsalt.
 10. The process for producing mercaptoalkyl phosphonium compoundsaccording to claim 9, wherein the halogenoalkyl phosphonium compound isa bromobutyl triphenylphosphonium compound, and the mercaptoalkylphosphonium compound is a mercaptobutyl triphenylphosphonium compound.